Ligand exchange reactions on thiolate-protected gold nanoclusters

As a versatile post-synthesis modification method, ligand exchange reaction exhibits great potential to extend the space of accessible nanoclusters. In this review, we summarized this process for thiolate-protected gold nanoclusters. In order to better understand this reaction we will first provide the necessary background on the synthesis and structure of various gold clusters, such as Au₂₅(SR)₁₈, Au₃₈(SR)₂₄, and Au₁₀₂(SR)₄₄. The previous investigations illustrated that ligand exchange is enabled by the chemical properties and flexible gold-sulfur interface of nanoclusters. It is generally believed that ligand exchange follows a S_N2-like mechanism, which is supported both by experiments and calculations. More interesting, several studies show that ligand exchange takes place at preferred sites, i.e. thiolate groups -SR, on the ligand shell of nanoclusters. With the help of ligand exchange reactions many functionalities could be imparted to gold nanoclusters including the introduced of chirality to achiral nanoclusters, size transformation and phase transfer of nanoclusters, and the addition of fluorescence or biological labels. Ligand exchange was also used to amplify the enantiomeric excess of an intrinsically chiral cluster. Ligand exchange reaction accelerates the prosperity of the nanocluster field, and also extends the diversity of precise nanoclusters.